CN111971433A - 生产经涂布的纸、纸板或膜的方法和经涂布的纸、纸板或膜 - Google Patents

生产经涂布的纸、纸板或膜的方法和经涂布的纸、纸板或膜 Download PDF

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Publication number
CN111971433A
CN111971433A CN201980025373.5A CN201980025373A CN111971433A CN 111971433 A CN111971433 A CN 111971433A CN 201980025373 A CN201980025373 A CN 201980025373A CN 111971433 A CN111971433 A CN 111971433A
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China
Prior art keywords
suspension
film
web
calender
paperboard
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CN201980025373.5A
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English (en)
Inventor
I.海斯卡宁
K.贝克福克
J.坎库宁
A.维托拉
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Stora Enso Oyj
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Stora Enso Oyj
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Publication of CN111971433A publication Critical patent/CN111971433A/zh
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Abstract

本发明涉及生产经涂布的纸、纸板或膜的方法，其中所述方法包括以下步骤；提供包含纤维素纤维和/或纳米纤维素的第一悬浮体；将第一悬浮体施加至基底上以形成纤维幅材，其中所述幅材具有第一和第二侧；提供包含聚合物和/或颗粒的第二悬浮体，其中在4重量％‑40重量％之间的干含量下第二悬浮体的布氏粘度高于3000mPas；提供至少一个压延机，其包含至少一个辊或带；将第二悬浮体施加到至少一个压延机辊或带的表面形成涂布幅材并且引导所述纤维幅材通过至少一个压延机，由此将涂布幅材施加至幅材的第一侧，形成经涂布的纸、纸板或膜。本发明还涉及根据所述方法生产的纸、纸板或膜。

Description

生产经涂布的纸、纸板或膜的方法和经涂布的纸、纸板或膜
技术领域
本发明涉及生产经涂布的纸、纸板或膜的方法，其中所述涂料包含聚合物和/或颗粒。本发明还涉及根据所述方法生产的经涂布的纸、纸板或膜。
背景技术
当从纸，纸板生产包装和制造待用于与包装相关的膜时，通常重要的是它们具有良好的阻隔性能。根据包装的最终用途，对阻隔性能和包装本身的要求是不同的。
在将涂布层施加至纸、纸板或膜时，为了改进产品的阻隔性能，重要的是控制涂布层向经涂布的产品中的渗透。通常不期望涂布层太深地渗透到基底产品中，因为这样会增加针孔或覆盖不充分的风险，并且可能无法为产品提供期望的阻隔性能。然而，优选的是涂布层部分渗透并且粘附至产品。在没有机械和物理化学粘合的情况下，位于表面上的涂料过多将导致产品分层的问题，例如在产品干燥或转换过程中。
进一步地，在施加涂布层时，所使用的悬浮体通常具有低的干含量，即需要的量较大以获得合适的流动性质。在用聚合物涂料(例如PVOH，CMC或淀粉)或包含纳米纤维素或微原纤化纤维素的涂料涂布纸、纸板或膜时，这通常构成问题。因此，需要找到一种解决方案，其中可以添加具有提高的干含量的涂料。
当从可再生资源生产可持续的膜用于包装应用时，现今可以生产出包含大量微原纤化纤维素的优良的阻隔膜。这例如描述在Aulin等，Oxygen and oil barrierproperties of microfibrillated cellulose films and coatings,Cellulose(2010)17:559-574，Lavoine等，icrofibrillated cellulose–Its barrier properties andapplications in cellulosic materials:A review,Carbohydrate polymers 90(2012)735-764和Kumar等，Comparison of nano-and microfibrillated cellulose films,Cellulose(2014)21:3443-3456中。
然而，难以生产包含大量的具有良好的阻隔性能和高强度(尤其是高撕裂强度)这两者的微原纤化纤维素的膜，尤其是薄膜。一种潜在的解决方案是生产包含微原纤化纤维素和较长的纤维素纤维这两者的膜。然而，已经发现较长的纤维的存在会使得膜的阻隔性能劣化。此外，微原纤化纤维素倾向于与较长的纤维牢固结合，导致在撕裂条件期间纤维被切割(而不是拉伸)，这不会改进膜的撕裂强度。进一步地，纤维素纤维可能影响膜的厚度和厚度变化。
因此需要生产这样的纸、纸板或膜，其包含聚合物和/或颗粒，比如具有良好的阻隔和强度性能这两者的纳米纤维素。并且其可以高效的方式生产。
发明内容
本发明的目标是提供向纸、纸板或膜的至少一侧提供包含聚合物和/或颗粒的涂布层的方法，所述方法消除了或缓解了现有技术方法中的至少一些缺点。
本发明由所附的独立权利要求定义。实施方式在所附的从属权利要求书和以下描述中提出。
本发明涉及生产经涂布的纸、纸板或膜的方法，其中所述方法包括以下步骤：提供包含纤维素纤维和/或纳米纤维素的第一悬浮体；将第一悬浮体施加至基底上以形成纤维幅材，其中所述幅材具有第一和第二侧；提供包含聚合物和/或颗粒的第二悬浮体，其中在4重量％-40重量％之间的干含量下，第二悬浮体的布氏粘度高于3000mPas，在10rpm的速度下并且在室温(23℃)下根据SCAN-P50:84测量；提供至少一个压延机，其包含至少一个辊或带；将第二悬浮体施加到至少一个辊或带的表面以形成涂布幅材并且引导所述纤维幅材通过至少一个压延机，由此将涂布幅材施加至幅材的第一侧，形成经涂布的纸、纸板或膜。
第一悬浮体优选包含在0.01重量％至20重量％之间的纳米纤维素，基于悬浮体的固体物的总干重量计。在生产纸或纸板产品时，纤维幅材可包含纳米纤维素(优选微原纤化纤维素)以向纸或纸板提供改进的强度性能。
第一悬浮体优选包含在70重量％至100重量％之间的纳米纤维素，基于悬浮体的固体物的总干重量计。因此，生产了包含纳米纤维素优选微原纤化纤维素的膜，其包含高含量的纳米纤维素，优选在70-100重量％之间的纳米纤维素，这涉及在添加最终的涂布层之前在膜本身中的纳米纤维素的量。
第二悬浮体的聚合物和/或颗粒优选为聚乙酸乙烯酯(PVAc)，聚乙烯醇(PVOH)，聚乙烯醇乙酸酯(PVOH/Ac)，乙烯乙烯基醇(EVOH)，聚偏氯乙烯(PVDC)，瓜尔胶，淀粉，半纤维素，纤维素衍生物，胶乳和/或纳米纤维素。
第二悬浮体优选包含10重量％至100重量％的聚合物和/或颗粒，例如PVOH，羧甲基纤维素，淀粉和/或纳米纤维素，或其混合物或其改性物，基于悬浮体的总干重量计。可为优选的是第二悬浮体包含在40-100重量％之间的聚合物和/或颗粒，基于悬浮体的总干重量计，甚至更优选在70-90重量％之间的聚合物和/或颗粒，基于悬浮体的总干重量计。因此，施加在纤维幅材上的涂料优选包含大量的聚合物和/或颗粒。这涉及在添加最终的额外涂布层之前涂料本身中的聚合物和/或颗粒的量。
第二悬浮体的纳米纤维素优选为改性的纳米纤维素。纳米纤维素优选为化学改性的纳米纤维素比如磷酸化的纳米纤维素，阳离子化的纳米纤维素，疏水化改性的纳米纤维素，二醛纳米纤维素，乙酰化的纳米纤维素，羧甲基化的纳米纤维素和/或TEMPO纳米纤维素。
第二悬浮体优选以导致形成0.1-20gsm，优选在0.5-10gsm之间的克重的涂层的量施加。已经发现通过向纸、纸板或MFC膜添加薄涂层，纸、纸板或膜的阻隔性能得到了改进。
所使用的压延机优选为具有扩展的压区(nip)的压延机。优选使用压延区域为至少20mm，优选压延区域为100-2000mm的扩展的压区。
压延机优选为带式压延机。所使用的带优选为金属带、聚合物带或经聚合物涂布的金属带。所述带还可含有其他表面层，比如陶瓷涂布层。
优选在0.1-200MPa，优选1-50MPa，最优选在1-10MPa之间的线荷载下对幅材进行压延。
压延机辊或带的表面的温度优选为在40-160℃之间，优选在60-90℃之间。可为优选的是压延机的表面的温度足够低以避免悬浮体在压延机辊或带的表面上沸腾。
所述方法可进一步包括以下步骤：将压延机的表面上的第二悬浮体干燥至在10-80重量％之间，优选在10-50重量％之间的干含量以形成涂布幅材。干燥可以通过使用外部加热设备来进行，例如通过空气加热或辐射固化和/或通过对压延机的表面加热。干燥意指去除水并且因此还包括脱水。
根据前述要求中任意项所述的方法，其中在将第二悬浮体施加至压延机辊或带的表面之前，第二悬浮体的温度高于40℃，优选高于60℃，优选在60-100℃之间，优选在60-90℃之间。所述方法可进一步包括在将幅材引导通过压延机之前，将形成的纤维幅材脱水至25-95重量％，优选在40-90重量％之间，甚至更优选在50-80重量％之间的干含量的步骤。可为重要的是，纤维幅材的干含量不是过低的使得可将纤维幅材引导通过压延机并且可添加第二悬浮体和形成涂布层。如果干含量过低，则纤维幅材在被引导通过压延机时可能会破裂。如果干含量过高，则所述工艺成本效益不高并且涂布层的粘附可能被劣化。
所述方法可进一步包括将表面胶料、泡沫涂料或包含聚合物的分散体涂料施加至纸、纸板或膜的任意侧，优选施加至纸、纸板或膜的第二侧的步骤。通过将表面胶料，泡沫涂料和/或分散体涂料施加至纸、纸板或膜，可改进例如纸、纸板或膜的热密封性能和/或耐水性或水以及水汽的阻隔性能。
所述方法可进一步包括将聚合物层施加至纸、纸板或膜的第二侧的步骤，通过层压聚合物膜或通过挤出聚合物的涂料进行。通过添加聚合物层，可以低成本生产具有例如热密封性能和/或阻隔性能的纸、纸板或膜。
本发明还涉及通过以上描述的方法获得的经涂布的纸或纸板。
本发明还涉及通过以上描述的方法获得的包含聚合物和/或颗粒的经涂布的膜。
经涂布的膜的克重优选低于45gsm，优选低于35gsm，甚至更优选低于30gsm。所述膜的密度优选高于700kg/cm3。所述膜的根据ASTM D-3985的透氧率(OTR)值(23℃，50％相对湿度)优选低于100cc/m2*天*atm，抗撕裂强度高于2.0Nm2/g，根据ISO 1974(Elmendorf方法)以几何MD/CD平均值测量并且优选地，膜的第一侧的根据ISO 8791-4的表面粗糙度PPS值低于10μm，优选低于5μm，最优选低于2μm。
根据本发明的膜优选是薄的半透明或透明的膜，其具有高密度，高光滑度，良好的阻隔性能和良好的强度。
具体实施方式
已经发现可生产具有良好的阻隔性能和良好的强度性能这两者的经涂布的纸、纸板或膜产品。可向纸、纸板或膜提供根据本发明的涂层。所述涂层通过将包含聚合物和/或颗粒的第二悬浮体(其中在4重量％-40重量％之间的干含量下，第二悬浮体的布氏粘度高于3000mPas)添加到至少一个压延机辊或带的表面而施加。所述第二悬浮体会在压延机辊或带的表面上形成涂布幅材。然后，以使得涂布幅材被添加至纤维幅材的方式将纤维幅材引导通过压延机。本发明的优点在于与第二悬浮体以被喷洒的悬浮体的形式添加或以任意其他方式直接添加至纤维幅材的情形相比，涂布幅材的干含量可被提高。因此，添加至纸、纸板或膜的水的量被降低。与根据现有技术的方法相比，通过本发明可施加粘度更高或干含量更高的悬浮体。
进一步地，所生产的纸、纸板或膜的表面会具有改进的光泽度，其来自压延机中的处理并且有光泽的表面会改进产品的阻隔性能以及印刷性能这两者。本发明的另一优点在于其更容易控制涂布层向纤维幅材中的渗透。以此方式，实现了更有效的材料利用，更好的品质，更少的由干燥引起的效应的问题等。其原因在于以下两者，可在不劣化涂布幅材的阻隔性能的情况下提高施加的涂布幅材的干含量，和在压延机处理期间可施加压力和热。因此，已发现可控制涂布幅材在纤维幅材上的渗透以避免涂布幅材过深地渗透到纤维幅材中，这会降低产品的阻隔性能，或避免涂布幅材位于纤维幅材的表面上，即渗透发生的过浅，这会导致降低的强度和分层的问题。
进一步地，可提高生产根据本发明的经涂布的纸、纸板或膜的生产速度。
第二悬浮体的布氏粘度高于3000mPas，优选在3000-100000m之间，根据SCAN-P50:84在4重量％-40重量％之间的干含量下测量。粘度测量在室温(23℃)下并且在10rpm的速度下进行。当施加至辊或带的表面时，所使用的第二悬浮体的粘度基于所使用的特定的应用(施加)方法而确定，在施加时的第二悬浮体的粘度不必然需要高于3000mPas。例如，第二悬浮体的干含量可被降低以降低粘度。然而，在4-40重量％之间的干含量第二悬浮体的粘度高于3000mPas(在室温和10rpm下)。
第二悬浮体的聚合物优选为水溶性聚合物，比如聚乙酸乙烯酯(PVAc)，聚乙烯醇(PVOH)，聚乙烯醇乙酸酯(PVOH/Ac)，乙烯乙烯基醇(EVOH)，瓜尔胶，淀粉(包括改性淀粉，比如糊精)。第二悬浮体的聚合物还可为非水溶性聚合物，比如聚偏氯乙烯(PVDC)和/或半纤维素，比如木聚糖或葡甘露聚糖。第二悬浮体的聚合物还可为纤维素衍生物，比如羧甲基纤维素和/或羟乙基纤维素。第二悬浮体的聚合物还可为胶乳，比如苯乙烯丁二烯共聚物或例如丙烯酸酯和/或苯乙烯的其他共聚物。
第二悬浮体的颗粒优选为纳米纤维素。
涂布幅材意指在压延机辊或带的表面上形成的涂层(涂料)，幅材或膜或浓缩的悬浮体(凝胶状)。
纤维幅材可以是多层纤维幅材。用于形成各层的第一悬浮体可具有不同的组成，即它们可包含不同的纤维和/或添加剂等以生产对于各层而言具有期望的性能的多层产物(产品)。可例如使用多层流浆箱生产纤维幅材，在多层流浆箱中第一悬浮体以多于一层的方式施加而形成多层纤维幅材。
所使用的压延机优选为具有扩展的压区的压延机。令人惊讶地发现通过使用具有扩展的压区的压延机，可以这样的方式简便地控制压延处理，使得所施加的涂布幅材的渗透是最优的，即所述幅材没有过深地或过浅地渗透到纤维幅材中。进一步地，改进了幅材的光泽度，阻隔性能以及粘附性。进一步地，如果具有高松厚度的产品得到了改进，那么更容易通过使用本发明来保持产品的松厚度。优选使用压延区域为至少20mm，优选压延区域为100-2000mm的扩展的压区。
所述压延机优选为带式压延机并且所使用的带优选为金属带，聚合物带或经聚合物涂覆的金属带。将第二悬浮体添加至带的表面。优选在0.1-200MPa，优选1-50MPa，更优选1-10MPa的线荷载下对所述幅材进行压延。基于基底、所施加的涂布幅材以及所生产的产品的最终用途来选择最优线荷载。还可使用具有一个或多个压力峰值的压区压力分布(profile)，其中例如，压区压力在压区的开端处较低并且在压区的末端处较高。
压延机的表面温度为在40-160℃之间，优选在60-90℃之间。提高的温度使得可控制涂布幅材的干含量以及所生产的产品的表面光泽度这两者。
压延机辊或带的表面意指与压延机中的纤维幅材接触的表面。因此，其可直接施加至辊或压延机的滚筒的表面或直接施加至带。
可将多于一种悬浮体施加至压延机辊或带的表面，即以形成多层涂布幅材。这可通过将多于一种悬浮体施加至压延机辊或带的表面而进行，例如通过随后的喷嘴。用于形成多层涂布幅材的多种悬浮体可以是相同的，或可优选在不同的层中使用包含例如不同添加剂的不同悬浮体。
所使用的压延机包含至少一个辊或带，所述纤维幅材被引导至该至少一个辊或带并且在至少一个辊或带处进行压延处理。所述压延机优选包含至少两个辊和/或带，在所述至少两个辊和/或带之间形成压区，并且引导纤维幅材通过所述压区。还可用第三悬浮体在第二侧上对经涂布的纸，纸板或膜进行涂布。第三悬浮体可被施加至压延机中的第二辊或带的表面或被施加至第二压延机的辊或带的表面。所述第二压延机优选直接位于第一压延机之后以向产物的第二面提供涂布幅材。因此，可使用多于一个，例如两个，三个或四个压延机以将多于一种涂布幅材施加在纤维幅材上。以此方式，可生产在两侧上都被涂布的产品。还可以在第二压延机中将第二涂布幅材施加在第一涂布幅材/层上以提供多层涂层。可优选在各压延机上使用不同的悬浮体，即第二悬浮体具有一定的含量，而第三悬浮体具有另一种含量等。以此方式，可定制产物并且能够在不同的层中使用不同的添加剂。
所述方法可进一步包括以下步骤：将压延机的表面上的第二悬浮体干燥至在10-50重量％之间的干含量以形成涂布幅材。干燥可通过使用外部加热设备来进行，例如通过空气加热或辐射加热/固化或通过对压延机的表面进行加热。
根据前述要求中任意项所述的方法，其中在将第二悬浮体施加至压延机辊或带的表面之前，第二悬浮体的温度高于40℃，优选高于60℃，优选在60-90℃之间。已发现在将第二悬浮体施加至压延机辊或带的表面之前，通过提高第二悬浮体的温度，可以显著更快的方式促进和进行悬浮体的干燥和涂布幅材的形成。
在添加至压延机辊或带的表面之前，还可使第二悬浮体脱气。第二悬浮体中存在的气泡可引起形成的涂布幅材中的针孔，这会劣化纸、纸板或膜上的涂层的阻隔性能。
在将幅材引导通过压延机之前，所述方法可进一步包括将形成的纤维幅材脱水至25-95重量％，优选在40-90重量％之间，甚至更优选在50-80重量％之间的干含量的步骤。可为重要的是纤维幅材的干含量不是过低的使得可将纤维幅材引导通过压延机并且可添加第二悬浮体和形成涂布层。如果干含量过低，则纤维幅材在被引导通过压延机时可能会破裂。如果干含量过高，则所述方法就没有成本效益并且涂布层的粘附可劣化。可以任何已知方式进行脱水。例如，可在丝网上或在例如压榨部上或通过以任何已知方式施加热或辐射来进行脱水。因此，干燥也包括在脱水中，并且可使用任何已知的干燥设备来实现幅材的期望的干含量。还可向纤维幅材添加水分以控制幅材的干含量。可优选向与压延机中的处理相关的纤维幅材添加蒸气，即在压延机中处理纤维幅材之前或期间。所添加的蒸气可随后用于提高幅材的水分含量以及还有提高纤维幅材的温度这两者。
纤维幅材通过将第一悬浮体施加在基底上而形成。基底可以是造纸机中的多孔丝网。因此可在造纸机的湿部中应用所述方法。然后，可在丝网上将形成的纤维幅材引导通过压延机或其可从丝网上移除并且然后被引导通过压延机，优选在基底上。在压延机中在处理之前可对纤维幅材进行任意类型的处理，例如脱水或干燥，例如在压榨部中以使得纤维幅材在压延机中处理之前得到期望的性能。造纸机意指本领域技术人员已知的用于制造纸、纸板纸巾或任意类似产品的任意类型的造纸机。
所述基底还可以是聚合物或金属基底。然后，优选将纤维幅材流延在聚合物或金属基底上。然后，可以任意常规方式将经流延的纤维幅材干燥，并且随后将其从基底上剥离。随后，将被剥离的纤维幅材引导通过根据本发明的压延机。还可在载体上(在该载体上将纤维幅材流延)将经流延的纤维幅材引导通过压延机。
将第二悬浮体添加至压延机辊或带的表面，即添加至滚筒或压延机的带的表面。通过接触或非接触涂布方法(比如喷洒)来添加第二悬浮体。涂料还可通过任意已知方式添加并且随后通过合适的设备(比如刮浆刀)在表面上水平化。所添加的第二悬浮体在压延机辊或带的表面上形成平坦的涂布幅材。形成涂布幅材的所添加的第二悬浮体随后被施加至纤维幅材的第一侧并且经涂布的纤维幅材随后在穿过压延机时在压延机中被处理。
添加至压延机辊或带的表面的第二悬浮体的干含量优选为在0.5-30重量％之间，优选在1-10重量％之间。所添加的第二悬浮体的干含量则可通过在压延机辊或带的表面上干燥悬浮体而提高。干燥压延机辊或带的表面上的第二悬浮体可通过使用外部加热进行，例如通过使用经加热的空气或本领域技术人员已知的其他方案。还可加热压延机辊或带的表面并且以此方式干燥第二悬浮体以形成涂布幅材。在将形成的涂布幅材施加至纤维幅材之前，形成的涂布幅材的干含量优选为在5-80重量％之间，优选在10-60重量％之间并且甚至更优选在15-40重量％之间。
压延机辊或带的表面会与纤维幅材的第一侧接触，这意味着间接接触，因为形成的涂布幅材会位于纤维幅材的第一侧和压延机辊或带的表面之间。
光学性能，比如纸、纸板或膜的光泽度，也得到了改进。这可在压延机中处理纸、纸板或膜之后肉眼看到。
纸或纸板意指任意类型的纸或纸板产品。纸或纸板包含纤维素纤维。可使用任意类型的纤维素纤维，即可使用阔叶木和/或针叶木纤维两者。纤维素纤维可从任意类型的纸浆纤维制成例如化学浆纤维，比如牛皮纸浆纤维，溶解纸浆，机械纸浆纤维和/或热磨机械纸浆纤维，NSSC，或脱墨纸浆，或再生纸浆。
膜意指具有良好的气体，气味或油脂或油阻隔性能，优选氧气阻隔性能的薄基底。经涂布的膜优选具有小于40g/m2的定量和范围为700-1400kg/m3的密度。克重为30g/m2的经涂布的膜的在23℃和50％的相对湿度下的根据ASTM D-3985的透氧率(OTR)值优选低于30cc/m2*天*atm。
第一悬浮体优选包含在0.01重量％至20重量％之间的纳米纤维素，基于悬浮体的固体物的总干重量计。在生产纸或纸板产品时，纤维幅材可包含纳米纤维素以向纸或纸板提供改进的强度性能。可为优选的是所述纳米纤维素为微原纤化纤维素。优选的是在生产经涂布的纸或纸板产品时，第一悬浮体还包含不同于纳米纤维素的其他纤维素纤维。优选的是第一悬浮体包含80-99重量％的纤维素纤维，基于悬浮体的固体物的总干重量计(除了被添加的纳米纤维素)。优选的是第一悬浮体包含90-100重量％的纤维素纤维，基于悬浮体的固体物的总干重量计(包括纳米纤维素)。
在生产膜时，优选的是第一悬浮体包含大量的纳米纤维素，甚至更优选微原纤化纤维素。因此可生产仅包含纳米纤维素的膜，即不存在任何其他纤维素纤维。第一悬浮体优选包含在70重量％至100重量％之间的纳米纤维素，基于悬浮体的总干重量计。因此，所生产的纳米纤维素膜包含大量的纳米纤维素，优选在70-100重量％之间的纳米纤维素，这涉及在添加最终的涂布层之前在膜本身中的纳米纤维素的量。
第一和第二悬浮体中的纳米纤维素优选为微原纤化纤维素(MFC)。第一悬浮体的纳米纤维素纤维的Schopper-Riegler(SR)值优选低于90，优选在60-90之间或甚至更优选在70-85之间。优选地，第一悬浮体中至少50％的纳米纤维素，更优选多于75％或甚至更优选多于85％的纳米纤维素的SR值低于90。优选地，第一悬浮体中至少50％的纳米纤维素，更优选多于75％或甚至更优选多于85％的纳米纤维素的SR值在70-85之间。Schopper-Riegler值可通过定义在EN ISO 5267-1中的标准方法获得。因此，第一悬浮体的纳米纤维素优选较粗大，这会改进纤维幅材的脱水。第一悬浮体还可包含Schopper-Riegler(SR)值高于90的纳米纤维素。第一悬浮体还可包含较长的纤维素纤维，阔叶木或针叶木纤维，优选牛皮纸浆针叶木纤维。第一悬浮体还可包含其他添加剂，比如留着化学品，颜料，羧甲基纤维素钠(CMC)，留着化学品，固定剂，胶体二氧化硅(留着化学品)，消泡剂，湿强度剂或干强度剂，淀粉等。
第二悬浮体优选包含在10重量％至100重量％之间，优选在40-100重量％之间并且甚至更优选在70-90重量％之间的聚合物和/或颗粒，基于悬浮体的总干重量计。因此，可为优选的是所生产的纸、纸板或膜的涂布层包含大量的聚合物和/或颗粒，这涉及在添加最终的额外涂布层之前在涂布层本身中的聚合物和/或颗粒的量。
第二悬浮体的纳米纤维素的Schopper Riegler(SR)优选高于85，优选高于90。优选地，第二悬浮体中至少50％的纳米纤维素，更优选多于75％或甚至更优选多于85％的纳米纤维素的SR值高于85。因此，第二悬浮体包含非常细小的纳米纤维素。Schopper Riegler值可通过定义在EN ISO 5267-1中的标准方法获得。第二悬浮体还可包含其他添加剂，比如颜料，羧甲基纤维素(CMC)，淀粉，光学增亮剂，染料，润滑剂，疏水试剂，湿强度剂或干强度剂，生物活性化学品，分散剂等。
第二悬浮体优选以形成具有0.1-20gsm，优选在0.5-10gsm之间的克重的涂层的量施加。在纸、纸板或膜上形成的涂层非常薄。已经发现通过向纸、纸板或膜添加薄涂层，改进了纸、纸板或膜的阻隔性能。形成的涂层的厚度可根据本领域技术人员已知的方法从形成的产品的断面图像分析测定。还可通过分析涂布步骤期间的转移效率(即在涂布之前和之后的压延机辊或带的表面量)来估算涂层的重量。这可通过多种方法进行，例如通过光学手段或光谱手段。
被引导至压延机的幅材的干含量优选在40-95重量％之间，更优选在50-85重量％之间。在丝网上形成幅材可因此以任意常规的方式被干燥或脱水，例如通过压榨或常规滚筒干燥，通过使用真空和/或通过使用热空气，以使其在被引导至压延机之前具有合适的干含量。
在被引导通过压延机之后生产的经涂布的纸、纸板或膜的干含量优选高于70重量％，甚至更优选高于80重量％，优选在85-97重量％之间。所生产的经涂布的纸、纸板或膜还可在被压延之后在额外的干燥步骤中被干燥。可使用任意常规干燥设备。如果要向经涂布的纸、纸板或膜添加额外的层，比如聚合物或金属层，则纸、纸板或膜的干含量是非常重要的。
纳米纤维素意指微原纤化纤维素(MFC)和/或纳米晶纤维素中的任一种。
可为优选的是在第二悬浮体中使用的纳米纤维素是改性的。取决于改性，改性的纳米纤维素会具有不同的性能。因此，通过使用不同的改性的纳米纤维素，可赋予产物不同的性能。因此，取决于产物的最终用途，使用具有合适性能的改性的纳米纤维素可为有利的。所述纳米纤维素优选为化学改性的纳米纤维素比如磷酸化的纳米纤维素，阳离子化的纳米纤维素，疏水化改性的纳米纤维素，二醛纳米纤维素，乙酰化的纳米纤维素，羧甲基化的纳米纤维素和/或TEMPO纳米纤维素。
微原纤化纤维素(MFC)在本专利申请的文中是指纳米尺度的纤维素颗粒纤维或至少一个维度小于100nm的纤丝。MFC包含部分或全部原纤化的纤维素或木质纤维素纤维。被释放的纤丝直径小于100nm，而实际的纤丝直径或粒径分布和/或纵横比(长度/宽度)取决于来源和制造方法。最小的纤丝被称为基元纤丝且直径为约2-4nm(见例如Chinga-Carrasco,G.,Cellulose fibres,nanofibrils and microfibrils,：The morphologicalsequence of MFC components from a plant physiology and fibre technology pointof view,Nanoscale research letters 2011,6：417)，同时常见的是基元纤丝的附聚形式，也称作微纤丝(Fengel，D.，Ultrastructural behavior of cell wallpolysaccharides，Tappi J.，March 1970，Vol 53，No.3.)，是当通过使用延长精磨方法或压降解离方法制造MFC时得到的主产物。取决于来源和制造方法，纤丝的长度可在约1微米至约10微米变化。粗MFC等级(grade)可能含有显著分数的原纤化的纤维，即从管胞(纤维素纤维)突出的纤丝，和一定量的从管胞(纤维素纤维)释放出的纤丝。
MFC存在不同的缩写，比如纤维素微原纤丝、原纤化纤维素、纳米原纤化纤维素、原纤丝附聚物、纳米尺度纤维素纤丝、纤维素纳米纤维、纤维素纳米纤丝、纤维素微纤维、纤维素纤丝、微原纤纤维素、微纤丝附聚物和纤维素微纤丝附聚物。MFC的特征还在于物理或物理化学性质，比如高表面积或其在分散在水中时在低固体物条件下(1-5重量％)形成凝胶状材料的能力。优选将纤维素纤维原纤化至这样的程度，所形成的MFC的最终比表面积为约1至300m2/g，或更优选50至200m2/g，当用BET方法为冷冻干燥的材料测定时。
存在多种制造MFC的方法，比如单次或多次精磨、预水解后接纤丝的精磨或高剪切解离或释放。通常需要一个或多个预处理步骤以便使得MFC制造能量有效且为可持续的。因此，可将待提供的纸浆的纤维素纤维用酶或化学方式预处理，例如水解或使纤维溶胀或减少半纤维素或木质素的量。在原纤化之前可将纤维素纤维化学改性，其中纤维素纤维含有不同于(或多于)原始纤维素中存在的官能团。这样的基团包括羧甲基(CMC)、醛基和/或羧基(通过N-氧基接到的氧化，例如“TEMPO”)、或季铵(阳离子纤维素)。在用上述方法之一改性或氧化之后，更容易将纤维解离成为MFC或纳米原纤尺寸或NFC。
纳米纤丝纤维素可含有一些半纤维素；该量取决于植物来源。经预处理的纤维(例如经水解、预溶胀、或氧化的纤维素原材料)的机械解离，用合适的设备进行，比如精磨机、研磨机、均质机、胶体排除装置(colloider)、摩擦研磨机、超声超声波仪、单螺杆或双螺杆挤出机、流化器比如微流化器，宏观流化器或流化器型均质机。取决于MFC制造方法，产物还可能含有细料(fines)、或纳米结晶纤维素，或例如其他存在于木纤维或造纸方法中的化学品。产物还可能含有各种量的未被有效原纤化的微米尺寸的纤维颗粒。
从木纤维素纤维，从阔叶木或针叶木纤维两者生产MFC。其还可由微生物来源、农业纤维制备，麦草浆，竹子，甘蔗渣或其他非木纤维来源被制得。其优选从包括来自原生纤维的纸浆的纸浆制得，例如机械、化学和/或化学热机械浆。其还可从损纸或再生纸制得。
以上描述的MFC定义包括，但不限于对纤维素纳米原纤丝(CNF)新提出的TAPPI标准W13021，其定义了含有多个具有结晶和无定型区域的基元纤丝、且具有高纵横比的纤维素纳米纤维材料，其中宽度为5-30nm且纵横比通常大于50。
第一和/或第二悬浮体还可包含湿强度剂，即可将湿强度剂添加至悬浮体。湿强度化学品通过使微原纤化(纤维素)交联来改进幅材的强度性能并且由此改进纸、纸板或膜的强度性能。可添加不同的湿强度剂，比如脲醛树脂(UH)，三聚氰胺甲醛树脂(MF)，聚酰胺-表氯醇(PEA)，乙二醛和/或聚丙烯酰胺(PAM)，或其混合物。
第一和/或第二悬浮体还可包含交联剂。通过将交联剂添加至第一悬浮体，纸、纸板或膜会在高相对湿度(RH)值具有改进的阻隔性能。可添加不同的交联剂，比如柠檬酸，多异氰酸酯/盐，金属离子优选碱土金属离子，阴离子-阳离子复合物和/或聚电解质复合物。
根据本发明的方法可进一步包括将表面胶料、泡沫涂料和/或包含聚合物的分散体涂料施加至纸、纸板或膜的一侧的步骤，优选施加至纸、纸板或膜的第二侧。所施加的涂料，例如表面胶料、泡沫涂料或分散体涂料使得可生产具有改进的阻隔性能的纸、纸板或膜。包含表面胶料，泡沫涂料或分散体涂料的纸、纸板或膜可具有改进的热密封性能和/或耐水性和水分阻隔性能。表面胶料，泡沫涂料或分散体涂料的聚合物优选为热塑性聚合物，比如聚乙烯(PE)，乙烯共聚物，基于丙烯酸酯的粘合剂比如基于甲基丙烯酸酯的粘合剂，基于苯乙烯的粘合剂例如苯乙烯-烯烃共聚物，基于乙烯基的粘合剂，例如PVC或PVcD。涂料还可包含会进一步改进热密封性性能的添加剂。涂料中的添加剂的实例为蜡，防滑剂(例如PE蜡，巴西棕榈蜡)，用于抗粘连、用于触觉/光学、用于粘度控制的颜料或无机填料，例如二氧化硅，滑石，PCC，抗氧化剂，UV稳定剂，光学增亮剂(OBA)，消泡剂和/或粘附促进剂。涂料优选在单一的步骤中添加以形成单层涂层，但其也可在多于一个步骤中添加以形成多层涂层。
根据本发明的方法可进一步包括将聚合物层施加至纸、纸板或膜的不与压延机直接接触的一侧步骤，即纸、纸板或膜的第二侧，通过聚合物膜的层压或通过聚合物的挤出涂布进行。聚合物层的添加使得可以低成本生产具有良好的阻隔性能，具有热密封性能的纸、纸板或膜。所述聚合物优选为热塑性聚合物。所述热塑性聚合物可是以下中的任一种：聚乙烯(PE)，聚对苯二甲酸乙二酯(PET)和聚乳酸(PLA)。聚乙烯可以是以下中的任一种：高密度聚乙烯(HDPE)和低密度聚乙烯(LDPE)，或其各种组合。通过使用例如PLA作为热塑性聚合物，所述产物可完全由可生物降解材料形成。
本发明还涉及通过以上描述的方法获得的经涂布的纸或纸板产品。
本发明还涉及通过以上描述的方法获得的包含聚合物和/或颗粒的经涂布的膜。
经涂布的膜的克重优选低于45gsm，优选低于35gsm或甚至更优选低于30gsm。优选的是膜的克重在10-40gsm之间，甚至更优选在10-30gsm之间。
经涂布的膜的密度高于优选高于700g/m3，优选在700-1400g/m3之间。
经涂布的膜的根据ASTM D-3985的透氧率(OTR)值(23℃，50％RH)优选低于100cc/m2*天*atm。因此，所生产的MFC膜具有非常良好的氧气阻隔性能。
经涂布的膜的抗撕裂强度优选高于2.0Nm2/g，根据ISO 1974(Elmendorf方法)以几何MD/CD平均值测量。
经涂布的膜的第一侧的根据ISO 8791-4的表面粗糙度PPS值优选低于10μm，甚至更优选低于5μm并且最优选低于2μm。已经发现通过本发明可生产具有非常光滑的表面的膜。如果金属层，比如铝层应当被附接至所述膜，表面光滑度是非常重要的。因此，根据本发明的膜适合于将金属层施加至所述膜的第一表面。
根据本发明的膜在包装干食品(比如谷物)时可用作盒子中的袋，可用作包装(包裹)基底，可用作纸、纸板或塑料中的层压材料，和/或可用作一次性电子产品的基底。
附图说明
图1:示出了根据本发明的方法的总体示意图。
附图具体说明
图1示出了根据本发明的方法的总体示意图。将包含纤维素纤维和/或纳米纤维素的第一悬浮体(1)引导至基底(2)，在基底(2)上形成纤维幅材(3)。基底(2)优选为造纸机或纸板制造机的多孔丝网。将基底(2)和纤维幅材(3)引导通过压延机(4)。向压延机带的表面(5)添加第二悬浮体(6)。然后，将第二悬浮体施加在纤维幅材(3)的第一侧上，该侧是与压延机(4)接触(经由通过第二悬浮体形成的涂布幅材)的一侧。以此方式，以非常简单且高效的方式生产经涂布的纸、纸板或膜。
鉴于以上对本发明的详细描述，其他修改和变型对于本领域技术人员将变得显而易见。然而，显然，可以在不脱离本发明的精神和范围的情况下进行这样的其他修改和变型。

Claims (23)

1.生产经涂布的纸、纸板或膜的方法，其中所述方法包括以下步骤：
-提供包含纤维素纤维和/或纳米纤维素的第一悬浮体，
-将第一悬浮体施加至基底上以形成纤维幅材，其中所述幅材具有第一和第二侧,
-提供包含聚合物和/或颗粒的第二悬浮体，其中在4重量％-40重量％之间的干含量下，第二悬浮体的布氏粘度高于3000mPas，在10rpm的速度下并且在室温(23℃)下根据SCAN-P50:84测量，
-提供至少一个压延机，其包含至少一个辊或带,
-将第二悬浮体施加到至少一个辊或带的表面形成涂布幅材，和
-引导所述纤维幅材通过至少一个压延机，由此将涂布幅材施加至幅材的第一侧，形成经涂布的纸、纸板或膜。
2.根据权利要求1所述的方法，其中第一悬浮体包含在0.01重量％至20重量％之间的纳米纤维素，基于悬浮体的总干重量计。
3.根据权利要求1所述的方法，其中第一悬浮体包含在70重量％至100重量％之间的纳米纤维素，基于悬浮体的总干重量计。
4.根据前述权利要求中任意项所述的方法，其中第二悬浮体的聚合物和/或颗粒包括聚乙酸乙烯酯(PVAc)，聚乙烯醇(PVOH)，聚乙烯醇乙酸酯(PVOH/Ac)，乙烯乙烯基醇(EVOH)，聚偏氯乙烯(PVDC)，瓜尔胶，半纤维素，淀粉，纤维素衍生物，胶乳，和/或纳米纤维素。
5.根据前述权利要求中任意项所述的方法，其中第二悬浮体包含10重量％至100重量％的聚合物和/或颗粒，基于悬浮体的总干重量计。
6.根据权利要求4或5所述的方法，其中第二悬浮体的纳米纤维素为改性的纳米纤维素。
7.根据前述权利要求中任意项所述的方法，其中以形成0.1-20gsm，优选在0.5-10gsm之间的克重的涂层的量施加第二悬浮体。
8.根据前述权利要求中任意项所述的方法，其中所述方法进一步包括在将幅材引导通过压延机之前，将形成的纤维幅材脱水至25-95重量％的干含量的步骤。
9.根据前述权利要求中任意项所述的方法，其中所使用的压延机为具有扩展的压区的压延机。
10.根据权利要求8所述的方法，其中压延机为带式压延机。
11.根据前述权利要求中任意项所述的方法，其中在0.1-200MPa，优选1-50MPa的线荷载下对幅材进行压延。
12.根据前述权利要求中任意项所述的方法，其中压延机辊或带的表面的温度为在40-160℃之间，优选在60-90℃之间。
13.根据前述权利要求中任意项所述的方法，其中所述方法进一步包括以下步骤：
-将压延机辊或带的表面上的第二悬浮体干燥至在10-80重量％之间的干含量以形成涂布幅材。
14.根据前述权利要求中任意项所述的方法，其中第二悬浮体的温度高于40℃。
15.根据前述权利要求中任意项所述的方法，其中所述方法进一步包括将表面胶料、泡沫涂料和/或包含聚合物的分散体涂料施加至纸、纸板或膜的第二侧的步骤。
16.根据前述权利要求中任意项所述的方法，其中所述方法进一步包括将聚合物层施加至纸、纸板或膜的第二侧的步骤，通过聚合物膜的层压或通过聚合物的挤出涂布进行。
17.通过权利要求1-2、4-16中任意项所述的方法获得的经涂布的纸或纸板。
18.通过权利要求1-2、3-16中任意项所述的方法获得的包含聚合物和/或颗粒的经涂布的膜。
19.根据权利要求18所述的膜，其中经涂布的膜的克重低于45gsm，优选低于35gsm。
20.根据权利要求18-19中任意项所述的膜，其中膜的密度高于700kg/cm3。
21.根据权利要求18-20中任意项所述的膜，其中膜的根据ASTMD-3985的透氧率(OTR)值(23℃，50％RH)低于100cc/m2*天*atm。
22.根据权利要求18-21中任意项所述的膜，其中膜的抗撕裂强度高于2.0Nm2/g，根据ISO 1974以几何MD/CD平均值测量。
23.根据权利要求18-22中任意项所述的膜，其中膜的第一侧的表面粗糙度PPS值低于10μm，优选低于5μm并且甚至更优选低于2μm，根据ISO 8791-4测量。
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